JP5180040B2 - Metal complexes of tridentate beta ketoiminates - Google Patents

Description

  This application claims priority from US patent application Ser. No. 11 / 945,678, filed Nov. 27, 2007.

  The semiconductor manufacturing industry uses metal-containing precursors to create conformal metal-containing films on substrates such as silicon, metal nitrides, metal oxides, and other metal-containing layers. There remains a need for new metal source containing precursors for chemical vapor deposition processes, including atomic layer deposition.

  The present invention is directed to metal-containing tridentate β-ketoiminates and solutions wherein the tridentate β-ketoiminates incorporate a nitrogen or oxygen functional group in the imino group. The tridentate β-ketoiminate is selected from the group represented by the following structural formulas (A) and (B).

Here, M is a metal from divalent to pentavalent. Examples of metals include calcium, magnesium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, vanadium, tungsten, manganese, cobalt, iron, nickel, ruthenium, zinc, copper, palladium, iridium, rhenium, and osmium. Can be given. Various organic groups can be used. For example, R ¹ is selected from the group consisting of alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl containing 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. R ² is selected from the group consisting of hydrogen, alkyl, alkoxy, alicyclic group, and aryl. R ³ is selected from the group consisting of alkyl, fluoroalkyl, alkoxyalkyl, alicyclic group, and aryl. R ⁴ comprises a C _3-10 branched alkyl or alkylene bridge having at least one chiral carbon atom, preferably 3 or 4 carbon atoms, and thus a 5- or 6-membered coordination ring to the metal center Is a group that forms R ⁵ and R ⁶ are individually selected from the group consisting of alkyl, fluoroalkyl, alicyclic group, and aryl, and these groups can be combined to form a ring containing carbon, oxygen, and nitrogen atoms. it can. The subscript n is an integer and is equal to the valence of the metal M.

Where M is a metal ion selected from Group 4, Group 5 metals including titanium, zirconium, and hafnium; R ¹ is alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl; Preferably selected from the group consisting of groups containing 1 to 6 carbon atoms; R ² is selected from the group consisting of hydrogen, alkyl, alkoxy, alicyclic groups, and aryl; R ³ is alkyl, Selected from the group consisting of alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl; R ⁴ is a C _3-10 branched alkyl or alkylene bridge having at least one chiral carbon atom, preferably 3 or 4 carbons include atom, a group forming a coordination ring 5- or 6-membered to the metal center; R ⁵ and R ⁶ are, independently, alkyl, fluoroalkyl, cycloaliphatic, a Is selected from the group consisting Lumpur, they together can form a ring containing carbon, oxygen, and nitrogen atom; R ⁷ is alkyl, fluoroalkyl, cycloaliphatic, and the group consisting of aryl M and n are each at least 1, and the sum of m + n is equal to the valence of the metal.

Several advantages can be achieved by using these metal-containing tridentate β-ketoiminates as precursors for chemical vapor deposition or atomic layer deposition. These benefits include the following:
Being able to form reactive complexes in good yields;
The ability to form monomeric complexes coordinated with a single ligand, especially calcium and strontium complexes, thereby achieving high vapor pressures;
By introducing a branched alkyl or alkylene bridge having at least one chiral carbon atom between two nitrogen atoms, the thermal stability of the resulting metal complex compared to those without a chiral center between the two nitrogen atoms. Ability to significantly increase
The ability to produce highly conformable metal films suitable for use in a wide variety of electrical applications;
The ability to produce highly conformable metal oxide thin films suitable for use in microelectronic devices;
The high chemical reactivity of the complex can enhance the surface reaction between the metal-containing tridentate β-ketoiminate and the substrate surface.

  The present invention is formed by deposition processes such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) on substrates such as silicon, metal nitrides, metal oxides, and other metal-containing layers. The present invention relates to metal-containing tridentate β-ketoiminate precursors and their solutions useful for making consistent metal-containing films. Such shape-matching metal-containing thin films have a variety of uses ranging from computer chips, optical devices, magnetic information storage media to metal catalysts coated on support materials. Unlike traditional tridentate β-ketoiminate precursors, this tridentate β-ketoiminate ligand incorporates at least one amino-organoimino functional group, and this has been reported in the literature as a donor ligand. In contrast, the most important point is that it contains a branched alkyl or alkylene bridge having at least one chiral carbon atom between two nitrogen atoms.

  Oxidizing agents for the vapor deposition process include oxygen, hydrogen peroxide, and ozone, and reducing agents for the vapor deposition process include hydrogen, hydrazine, monoalkyl hydrazine, dialkyl hydrazine, and ammonia.

  One type of structure of this metal precursor is represented by the following structural formula (1A) in which the metal M is divalent.

Here, M is selected from the metal atoms of the second, eighth, ninth, and tenth groups. In this precursor, preferably R ¹ is a C _4-6 alkyl group, preferably a t-butyl or t-pentyl group when the metal is strontium and barium, and a C when the metal is cobalt or nickel. It is _1-6; R ² is hydrogen, C _1-6 alkyl, and C _6-10 is selected from the group consisting of aryl; R ³ is C _1-6 alkyl, C _1-6 fluoroalkyl, and C _6- Selected from the group consisting of ₁₀ aryl; R ⁵ and R ⁶ are independently lower C _1-3 alkyl, preferably a methyl group; R ⁴ is a C _3-10 branched alkyl having at least one chiral carbon atom Or an alkylene bridge, preferably a group containing 3 or 4 carbon atoms. Preferred metals are calcium, strontium, barium, iron, cobalt and nickel.

  Another type of structure in the first class of metal complexes containing a tridentate beta-ketoiminate ligand is shown by the following structural formula (2A) where the metal M is trivalent.

Here, M is selected from Group 3 metal atoms. In this precursor, preferably R ¹ is a C _4-6 alkyl group, preferably t-butyl and t-pentyl groups; R ² is hydrogen, C _1-6 alkyl, and C _6-10 aryl. R ³ is selected from the group consisting of C _1-6 alkyl, C _1-6 fluoroalkyl, and C _6-10 aryl; R ⁵ and R ⁶ are independently lower C _{1- 3} alkyl, preferably a methyl group; R ⁴ is a C _3-10 branched alkyl or alkylene bridge having at least one chiral carbon atom, preferably a group containing 3 or 4 carbon atoms. Preferred metals are scandium, yttrium, and lanthanum.

  The second class of metal-containing precursors consists of tridentate beta ketoiinate ligands as shown in structural formula (B) below.

Here, M is a Group 4 or Group 5 metal such as titanium, zirconium, or hafnium. As shown, the complex consists of at least one alkoxy ligand and a tridentate beta-ketoiminate ligand having at least one aminoorganoimino functional group. Preferred R ^1-6 groups are the same as those in the structural formula (A). Preferred R ⁷ groups are linear or branched alkyls such as isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, m and n are at least 1, and the sum of m + n is the metal M Equal to valence.

  Tridentate beta-ketoiminate ligands are prepared by well-known procedures, for example, Claisen condensation of bulky ketones and ethyl esters in the presence of strong bases such as sodium amide or sodium hydride, followed by, for example, alkylaminoalkylamines. And can be prepared by other known procedures such as Schiff base condensation. The ligand can be purified by vacuum distillation for liquids and crystallization for solids.

Preferred methods for high yield formation of thermally stable tridentate ligands include bulky R ¹ groups, such as C _4-6 alkyl groups without hydrogen attached to carbon bonded to ketone functional groups Is preferred. The most preferred R ¹ group is tert-butyl or tert-pentyl. The R ¹ group prevents side reactions from occurring in subsequent Schiff condensations and later protects the metal center from intermolecular interactions. There is a competing problem that the R ^1-7 group in the tridentate ligand must be as small as possible in order to reduce the molecular weight of the resulting metal-containing complex and allow the realization of complexes with high vapor pressures. That is not to be. Preferred R ⁴ is a branched alkyl or alkylene bridge having at least one chiral carbon atom, most preferably the resulting metal complex forms a 5- or 6-membered coordination ring with respect to the metal center and is stable. Is a group containing 3 or 4 carbon atoms. The chiral center in the ligand can play a decisive role in reducing the melting point and increasing the thermal stability.

  Next, a complex containing a metal can be prepared by a reaction of the obtained tridentate ligand with a pure metal, a metal amide, a metal hydride, and a metal alkoxide. The metal-containing complex also reacts the tridentate ligand with alkyl lithium or potassium hydride to produce the lithium or potassium salt of the ligand, followed by the metal halide, MXn (X = Cl, Br, I can also be prepared by reacting with n = 2, 3). Group 4 and 5 mixed ligand complexes can be made by changing the ratio of metal alkoxide to tridentate ligand.

  Metal-containing complexes with tridentate beta-ketoiminate ligands for making metal or metal oxide thin films at temperatures below 500 ° C by either chemical vapor deposition (CVD) or atomic layer deposition (ALD) methods It can be used as a precursor. While the CVD process can be performed with or without a reducing or oxidizing agent, the ALD process is usually performed with another reactant, such as a reducing or oxidizing agent.

  In the case of multi-component metal oxides, if these complexes have the same tridentate beta-ketoiminate ligand, they can be premixed. Metal-containing complexes with these tridentate beta-ketoiminate ligands can be fed to the CVD or ALD reactor in the vapor phase by well-known bubbling or vapor draw methods. The direct liquid delivery (delivery) method can also be used by dissolving the complex in a suitable solvent or solvent mixture and preparing a 0.001 to 2M molar solution depending on the solvent or solvent mixture used.

Solvents used to solubilize precursors for use in the vapor deposition process are aliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters, nitrites, and alcohols. The solvent component of the solution is preferably a glyme solvent having 1-20 ethoxy- (C ₂ H ₄ O) -repeating units; C ₂ -C ₁₂ alkanols, dialkyl ethers containing C ₁ -C ₆ alkyl moieties, C ₄ -C ₈ cyclic ethers; C ₁₂ -C ₆₀ crown O ₄ -O ₂₀ ethers (wherein the range of the pre been C _i is the number i of carbon atoms in the ether compound, a post The range of O _i is the number i of oxygen atoms in the ether compound); C ₆ -C ₁₂ aliphatic hydrocarbons; C ₆ -C ₁₈ aromatic hydrocarbons; An organic ester; an organic amine; a solvent selected from the group consisting of polyamines and organic amides.

Another class of solvents that offers advantages is a class of organic amides of the form RCONR'R ", where R and R 'are alkyls having 1-10 carbon atoms that are joined to form a ring. Can form the formula group (CH ₂ ) _n , where n is 4-6, preferably 5 and R ″ is selected from alkyl and cycloalkyl having 1 to 4 carbon atoms . Examples are N-methyl and N-cyclohexyl-2-pyrrolidinone, N, N-diethylacetamide, and N, N-diethylformamide.

  The following examples illustrate the preparation of metal-containing complexes of tridentate beta-ketoiminate ligands and their use as precursors in metal-containing thin film deposition processes.

Example 1
Synthesis of 2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanone

  11.68 g (114.34 mmol) of 1 in a solution of 13.55 g (95.29 mmol) of 2,2-dimethyl-3,5-hexanedione in 150 ml of tetrahydrofuran (THF) containing 20 g (140.81 mmol) of sodium sulfate. -Dimethylamino-2-propylamine was added. The reaction mixture was heated to 65 ° C. for 72 hours. Upon completion, the THF was evaporated under vacuum and the mixture was heated at 80 ° C. for 1 hour under a vacuum of 140 mTorr to distill off excess 1-dimethylamino-2-propylamine. Vacuum transfer heating of the residual oil was performed at 110 ° C. under a vacuum of 100 mTorr. 18.75 g of lime green yellow oil was obtained and GC analysis showed 99% purity. The yield was 87%.

¹ H NMR (500MHz, C ₆ D ₆ ): δ = 11.51 (s, 1H), 5.20 (s, 1H), 3.24 (m, 1H), 1.91 (m, 2H), 1.91 (s, 6H), 1.60 (s, 3H), 1.32 (s, 9H), 0.94 (d, 3H).

Example 2
Synthesis of bis (2,2-dimethyl-5- (1-diethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium

To a solution of 1 g (1.81 mmol) Sr (N (SiMe ₃ ) ₂ ) ₂ (THF) ₂ in 10 mL THF was added 0.82 g (3.62 mmol) 2,2-dimethyl-5 in 10 mL THF. -(1-Diethylamino-2-propylimino) -3-hexanone was added dropwise at room temperature. After stirring at room temperature for 16 hours, THF was evaporated under vacuum to give a gray solid that was taken up as a solution in hexane. Hexane was evaporated and the dried solid was recrystallized in pentane at room temperature. 0.48 g of transparent needle-like crystals were obtained (50% yield based on Sr).

Elemental analysis: Calculated for C26H50N4O2Sr: C, 58.01; N, 10.40; H, 9.36. Found: C, 56.07; N, 10.10; H, 8.86. ¹ H NMR (500 MHz, C ₆ D ₆ ): δ = 5.12 (s, 1H), 3.42 (m, 1H), 3.32 (t, 1H), 1.96 (b, 2H), 1.83 (s, 6H), 1.72 (b, 2H), 1.41 (s, 9H), 0.94 ( d, 3H).

  The structure of colorless crystals was revealed by single crystal analysis. The structure shows that strontium is coordinated to two oxygens and four nitrogens from two tridentate beta-ketoiminate ligands in a distorted octahedral environment.

This is illustrated in Figure 1, 2-propyl bridge between the two nitrogen atoms of the imino functionality for R ⁴ are present, shown as C4, C5 and C18, C17. C4 and C17 are chiral atoms because they are bonded to four different substituents, ie, for C4, H, N1, C11, and C5, and for C17, H, N3, C18, and C24 is there.

Figure 2 shows a TGA of the compound of Example 2 with 2-propyl bridges with chiral centers between the two nitrogen atoms of the imino functionality for R ^4; which, R ⁴ is also a chiral center In contrast to similar compounds that are not ethyl bridges. The compound of Example 2 is indicated by a solid line, and the analogous compound in which R ⁴ is an ethyl bridge is indicated by a dotted line. Large residues in TGA analysis are typical of less stable compounds. That is, the similar compound having no chiral center has a residue exceeding 14%, whereas the compound of Example 2 has a residue of less than 1%, which is used for depositing a metal-containing thin film by vapor deposition in semiconductor manufacturing. It shows that the thermal stability required for use as a precursor is greatly enhanced.

Example 3
Synthesis of bis (2,2-dimethyl-5- (1-methylethylamino-2-propylimino) -3-hexanonato-N, O, N ') nickel

A solution of 3.49 g (15.43 mmol) 2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanone in 10 mL hexane at -78 ° C. in a dry ice / acetone bath To this was added 6.17 mL (15.43 mmol) of 2.5M n-butyllithium in hexane dropwise. The solution was warmed to room temperature and stirred for 1 hour. Hexane was evaporated from the solution under vacuum to give a yellow oil that was sticky as a residue. To this residue was added 20 mL of THF and the resulting solution was added to 1.00 g (7.72 mmol) of NiCl ₂ in 10 mL of THF at room temperature. It stirred for 96 hours, heating at 60 degreeC under argon. The THF was evaporated under vacuum and the remaining dark green solid was taken up in hexane, heated and filtered. Hexane was evaporated under vacuum to give 3.5 g of a sticky dark green solid that was sublimed at 100 ° C. under a vacuum of 65 mTorr for 48 hours to give 2.8 g of a green solid (70% yield). The sublimated material was recrystallized by slow evaporation of pentane at room temperature.

  Elemental analysis: Calculated for C26H50N4NiO2: C, 61.30; H, 9.89; N, 11.00. Found: C, 59.18; H, 9.09; N, 10.84.

The structure of the dark green crystal was revealed by single crystal analysis. The structure shows that nickel is coordinated to two oxygens and four nitrogens from two tridentate beta-ketoiminate ligands in a distorted octahedral environment. This is illustrated in Figure 3, C9, 2-propyl bridge between the two nitrogen atoms of the imino functionality for R ⁴ is present, it indicated as C11 and C22, C24. C9 and C22 are chiral atoms because they are bonded to four different substituents, namely C, 9 for H, N1, C10, and C11, and C22 for H, N3, C23, and C24.

Figure 4 shows a TGA of the compound of Example 3 with 2-propyl bridges with chiral centers between the two nitrogen atoms of the imino functionality for R ^4; which, R ⁴ is also a chiral center In contrast to similar compounds that are not ethyl bridges. The compound of Example 3 is shown as a solid line and the analogous compound where R ⁴ is an ethyl bridge without a chiral center is shown as a dotted line. Large residues in TGA analysis are typical of less stable compounds. That is, a similar compound having no chiral center has a residue of more than 13%, whereas the compound of Example 3 has a residue of less than about 3%, so that a metal-containing thin film is deposited by vapor deposition in semiconductor manufacturing. It shows that the thermal stability required for use as a precursor of is greatly enhanced.

Example 4
Synthesis of Ti (O- ⁱ Pr) ₃ (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato

  To a solution of 1 g (3.52 mmol) titanium (IV) isopropoxide in 15 mL hexane, 0.80 g (3.52 mmol) 2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-Hexanone was added and the reaction mixture was heated at 60 ° C. for 16 hours. All volatile components were evaporated under vacuum to give 1.59 g of coarse granular oil.

¹ H NMR (500MHz, C ₆ D ₆ ): δ = 5.32 (s, 1H), 5.10 (b, 3H), 3.20 (m, 1H), 2.40 (b, 2H), 2.40 (b, 6H), 1.64 (s, 3H), 1.39 (d, 18H), 1.36 (s, 9H), 1.27 (b, 3H).

Example 5
Synthesis of 4- (1-dimethylamino-2-propylimino) -2-pentanone

To a solution of 10 g (199.76 mmol) acetylacetone in THF at room temperature with 20 g Na ₂ SO ₄ added, 24.49 g (239.1 mmol) 1-dimethylamino-2-propylamine was added. The slurry was stirred at room temperature for 16 hours, and the completion of the reaction was confirmed by GC / MS. All volatile components were evaporated under vacuum and unreacted acetylacetone and diamine were removed by heating at 60 ° C. for 2 hours under 100 mTorr vacuum. The yellow residual oil was purified by vacuum transfer heating at 130 ° C. under 100 mTorr vacuum. 13.5 g of a pale yellow oil was obtained as a pure product in a yield of 74%.

¹ H NMR (500MHz, C ₆ D ₆ ): δ = 11.25 (s, 1H), 4.90 (s, 1H), 3.22 (m, 1H), 2.06 (s, 3H), 1.96 (m, 2H), 1.93 (s, 6H), 1.54 (s, 3H), 0.92 (d, 3H).

Example 6
Synthesis of bis (4- (1-dimethylamino-2-propylimino) -2-pentanonato) strontium

To a solution of 1.0 g (1.81 mmol) Sr (N (SiMe ₃ ) ₂ ) ₂ (THF) ₂ in 15 ml THF at room temperature, 0.66 g (3.62 mmol) 4- (1-dimethylamino-2- Propylimino) -2-pentanone was added. The reaction mixture was stirred for 16 hours. Evaporation of all volatile components under vacuum yielded a foamy solid that was dissolved in hexane and evaporated again to give a gray solid weighing 0.76 g. The volatile component indicated that the reaction occurred in the presence of trimethylsilyldiamine. The crude solid was dissolved in hot hexane and filtered to give a pale yellow solution, which was slowly evaporated at room temperature to produce clear crystals.

  The structure of colorless crystals was revealed by single crystal analysis. The structure consists of two strontium atoms and four tridentate beta-ketomate ligands, each strontium atom coordinated with four nitrogen atoms and three oxygen atoms.

Example 7
Bis (4- (1-dimethylamino-2-propylimino) -2-pentanonato) nickel

A solution of 1.41 g (7.72 mmol) of 4- (1-dimethylamino-2-propylimino) -2-pentanone in 15 mL of hexane at -78 ° C with a drop of 3.09 mL (7.72 mmol) of nBu-Li. Added one by one. The solution was warmed to room temperature and stirred for 30 minutes. All volatiles were evaporated to a sticky yellow oil that was taken up in 10 mL of THF. To the resulting solution 0.5 g (3.86 mmol) NiCl ₂ in 10 mL THF was added via cannula. After about 20 minutes, the beige NiCl ₂ suspension turned black. The suspension was heated at 50 ° C. for 48 hours. All volatiles were evaporated under vacuum to give 1.7 g of a gray solid which was sublimed by heating at 100 ° C. under a vacuum of 65 mTorr for a week. The green solid was collected and recrystallized by slow evaporation in pentane to give green crystals.

  Elemental analysis: Calculated for C20H38N4NiO2: C, 56.49; N, 13.18; H, 9.01. Found: C, 56.62; N, 13.19; H, 9.13.

Single crystal analysis by X-ray confirmed that Ni atoms are coordinated with two tridentate keto ligands in an octahedral environment. This is shown in FIG. 5, where the nickel atom is coordinated with four nitrogen atoms (N1, N2, N3, N4) and two oxygen atoms (01, 02). In this example, R ¹ = Me, R ² = H, R ³ = Me, R ⁵ = R ⁶ = Me, and R ⁴ is C3, C4 for one ligand and C13 for another ligand. , 2-propyl bridge labeled C14. C4 and C14 bind to four different substituents: H for C4 (not shown), H for N2, C3 and C5, C14 (not shown), N4, C13 and C15 It is a chiral atom.

  FIG. 6 is a thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) diagram of the compound of Example 7, in which the complex with chiral centers is volatile, has less residue, and has a low melting point (˜100 C.) and that this complex can be used as a precursor for depositing nickel-containing thin films in a CVD or ALD process.

Example 8
Bis (4- (1-dimethylamino-2-propylimino) -2-pentanonato) cobalt

To a solution of 1.41 g (7.70 mmol) 4- (1-dimethylamino-2-propylimino) -2-pentanone in THF at −78 ° C., 3.08 mL (7.70 mmol) 2.5 MnBu-Li in hexane. One drop was added. The resulting slurry was warmed to room temperature and stirred for 2 hours, then added via cannula to a flask containing 0.50 g (3.85 mmol) CoCl ₂ in THF. The reaction mixture immediately turned coffee colored and was kept at 50 ° C. for 2 days. All volatile components were removed to give a dark brown foam that was taken up in hexane and evaporated to give 2.2 g of a dark brown solid.

Example 9
Tri (isopropoxy) (4- (1-dimethylamino-2-propylimino) -2-pentanonato) titanium

  To a solution of 1.00 g (3.52 mmol) titanium (IV) isopropoxide in 15 mL THF was added 0.65 g (3.52 mmol) 4- (1-dimethylamino-2-propylimino) -2-pentanone. . The reaction mixture was stirred at room temperature for 16 hours and then the THF was evaporated under vacuum. At the end of the treatment, 1.42 g of a granular oil was obtained with a yield of 99%.

Example 10
Synthesis of 2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanone

  To a solution of 8.54 g (60.06 mmol) 2,2-dimethyl-3,5-hexanedione in 100 mL THF, 8.60 g (60.06 mmol) 1-diethylamino-2-propylamine and 12 g (84.48 mmol). ) Sodium sulfate was added. The reaction mixture was heated to 60 ° C. for a week. All solids were removed and unreacted starting material was distilled off by heating to 75 ° C. under vacuum of 100 mTorr for several hours. Short path distillation yielded 13.16 g of lime green oil in 86% yield. GC measurements showed that the purity was> 99%.

¹ H NMR (500MHz, C ₆ D ₆ ): δ = 11.51 (s, 1H), 5.20 (s, 1H), 3.24 (m, 1H), 2.24 (m, 4H), 2.15 (dd, 1H), 2.01 (dd, 1H), 1.64 (s, 3H), 1.33 (s, 9H), 0.95 (d, 3H), 0.82 (t, 6H).

Example 11
Synthesis of bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium

  To a suspension of 1.00 g (4.86 mmol) strontium isopropoxide in 15 mL THF at room temperature was added 2.60 g (10.20 mmol) ligand P in 15 mL THF. The suspension became a solution after 10 minutes of stirring. After stirring for 16 hours at room temperature, the greenish yellow solution was placed under vacuum and the THF was evaporated to an oil. The oil was taken out as a solution in hexane and evaporated again to give 3.03 g of oil. When heated slightly, solids began to form from the oil. The mixture was heated in hexane and filtered through a syringe filter. 1.20 g of clear crystals were collected and the yield was 42%.

Elemental analysis: Calculated value of Sr (Me ₃ CCOCHCNMeCHCH ₂ NEt ₂ ) ₂ : C, 60.62; N, 9.42; H, 9.83. Found: C, 60.26; N, 9.47; H, 9.28.

¹ H NMR (500MHz, C ₆ D ₆ ): δ = 5.14 (s, 1H), 3.61 (m, 1H), 3.26 (t, 1H), 2.52 (m, 2H), 2.39 (b, 2H), 2.23 (dd, 1H), 1.87 (s, 3H), 1.41 (s, 9H), 1.02 (d, 3H), 0.76 (b, 6H).

The structure of colorless crystals was clarified by single crystal analysis. The structure shows that the strontium atom is coordinated with two 2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonate ligands in a distorted octahedral environment. ing. This is illustrated in FIG. 7, where the strontium atom is coordinated with four nitrogen atoms (N1, N2, N3, N4) and two oxygen atoms (01, 02). In this example, R ¹ = Bu ^t , R ² = H, R ³ = Me, R ⁵ = R ⁶ = Et, and R ⁴ is C1, C2 for one ligand and for another ligand 2-propyl bridges labeled C16 and C17. C2 and C17 are attached to four different substituents: H in the case of C2 (not shown), N2, C1 and C10, H in the case of C17 (not shown), N4, C16 and C25 It is a chiral atom.

Example 12
Synthesis of 2,2-dimethyl-5- (1-methylethylamino-2-propylimino) -3-hexanone

  To a solution of 6.00 g (42.19 mmol) 2,2-dimethyl-3,5-hexanedione in 75 mL THF was added 5.88 g (50.63 mmol) 1-methylethylamino-2-, followed by 10.00 g Of sodium sulfate was added. The reaction mixture was heated to 72 ° C. for 48 hours. GC showed the reaction was complete. THF was evaporated under vacuum. Unreacted diamine was distilled off by heating at 75 ° C. under a vacuum of 150 mTorr for 1 hour. The residue was purified by vacuum transfer heating at 120 ° C. under 100 mTorr vacuum. A lime green oil was isolated in an amount of 9.21 g. GC was shown to be a pure compound. Yield 91%.

¹ H NMR (500MHz, C ₆ D ₆ ): δ = 11.51 (s, 1H), 5.20 (m, 1H), 3.26 (m, 1H), 2.10 (m, 2H), 2.04 (dd, 1H), 1.97 (dd, 1H), 1.95 (s, 3H), 1.62 (s, 3H), 1.32 (s, 9H), 0.95 (d, 3H), 0.84 (t, 3H).

Example 13
Synthesis of bis (2,2-dimethyl-5- (1-methylethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium

  To a suspension of 1.00 g (4.86 mmol) of strontium isopropoxide in 45 mL of THF was added 2.45 g (10.20 mmol) of ligand Q in 5 mL of THF. The suspension went into solution after about 20 minutes. After stirring for 16 hours at room temperature, the THF was evaporated under vacuum to give 2.87 g of a yellow oil. The crude oil was heated at 140 ° C. under vacuum at 100 mTorr for 2 hours to remove free ligand. The icy residue was taken up in hexane and ground at -40 ° C to recover the solid. The solid was recrystallized by heating with dodecane to obtain 1.10 g of colorless crystals in a yield of 40%.

¹ H NMR (500MHz, C ₆ D ₆ ): δ = 5.14 (s, 1H), 3.51 (m, 1H), 3.31 (b, 1H), 2.49 (b, 1H), 2.15 (b, 1H), 1.85 (s, 3H), 1.79 (b, 1H), 1.41 (s, 9H), 1.30 (s, 3H), 0.98 (d, 3H), 0.80 (b, 3H).

The structure of colorless crystals was clarified by single crystal analysis. The structure shows that in a distorted octahedral environment, the strontium atom is coordinated to two 2,2-dimethyl-5- (1-methylethylamino-2-propylimino) -3-hexanonate ligands. Show. This is illustrated in FIG. 8, where the strontium atom is coordinated with four nitrogen atoms (N1, N2, N3, N4) and two oxygen atoms (01, 02). In this example, R ¹ = Bu ^t , R ² = H, R ³ = Me, R ⁵ = Me, R ⁶ = Et, and R ⁴ is another coordination as C5, C6 for one ligand. A 2-propyl bridge labeled as C19, C20 for the child. C5 and C19 bind to four different substituents: H in the case of C5 (not shown), N1, C6 and C11, H in the case of C19 (not shown), N3, C20 and C25 It is a chiral atom.

  FIG. 9 shows a thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) diagram of the compound of Example 13. The new Sr complex has a chiral center and an asymmetric substituent on the amino function. The large amount of residue in the TGA analysis symbolizes the poor thermal stability of the compound. Thus, the compound of Example 13 is less than approximately 5%, indicating that substantial improvement in thermal stability is required when used as a precursor to deposit metal-containing thin films in semiconductor processing deposition. Yes. DSC shows the lowest melting point (˜133 ° C.) among the conventionally synthesized tridentate beta-ketoiminate strontium complexes. The increased thermal stability and the lowest melting point are believed to be due to chiral centers as well as asymmetric substituents on the amino function.

Example 14
Synthesis of tris (4- (1-dimethylamino-2-propylimino) -2-pentanonato) lanthanum

  A solution of 0.52 g (1.64 mmol) lanthanum (III) isopropoxide in 15 mL THF was added to 0.90 g (4.93 mmol) 4- (1-dimethylamino-2-propylimino)-in 5 mL THF. 2-Pentanone was added. The resulting slightly yellow solution was stirred at room temperature for 1 hour. All volatile components were removed in vacuo to give approximately 1.00 g of a yellow solid in 88% yield.

Example 15
Tris (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato)
Synthesis of lanthanum

  A solution of 0.52 g (1.64 mmol) lanthanum (III) isopropoxide in 15 mL THF was added to 1.12 g (4.93 mmol) 2,2-dimethyl-5- (1-dimethylamino- in 5 mL THF. 2-propylimino) -3-hexanone was added. The slightly yellow solution was stirred at room temperature for 3 days. All volatile components were removed in vacuo to give approximately 1.20 g of a yellow solid in 90% yield.

Example 16
Tris (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato)
Yttrium synthesis

  A cloudy suspension of 1.00 g (3.76 mmol) Y-isopropoxide in 20 mL THF was added to 2.55 g (11.27 mmol) 2,2-dimethyl-5- (1-dimethyl) in 5 mL THF. Amino-2-propylimino) -3-hexanone was added. The resulting cloudy yellow solution was refluxed for 3 hours. All volatile components were removed in vacuo to give approximately 2.50 g of a yellow solid in 87% yield.

  One of the critical requirements for a precursor used in chemical vapor deposition and atomic layer deposition is that the precursor must be stable at the feed temperature, generally in the range of 40-150 ° C. . Thermogravimetric analysis (TGA) is widely used as a tool for screening compounds. Measurements were made in an open aluminum crucible with a sample size in the dry box of 10-20 mg. The temperature increase rate is usually 10 ° C./min. As the temperature increases, the compound begins to evaporate, decompose, or both. Pure evaporation produces almost no residue, but evaporation plus decomposition produces some residue. In general, less residue in the TGA diagram indicates that the compound is more thermally stable and is therefore more suitable as a precursor for making thin films. As shown in FIGS. 2 and 4, the compounds disclosed in the present invention have much less residue, are thermally more stable, and can function better as precursors than conventional similar compounds. It is shown that.

  The introduction of chiral centers is one approach to increase thermal stability and simultaneously lower the melting point of the resulting metal compound. A molecule is chiral when it cannot be superimposed on its mirror image, and the two mirror images of such a molecule are called enantiomers. When four different substituents are attached to a carbon atom, it is chiral. In the compounds of Examples 2 and 3, there are two chiral carbon atoms that coexist in the solid state with three enantiomers and weaken the intermolecular interaction, thus increasing the volatility of the compound. Let For example, as shown in FIG. 10, bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ′) strontium is bis (2,2-dimethyl- It is less volatile than 5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N ′) strontium. Note that bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium is bis (2,2-dimethyl-5- (dimethyl Aminoethyl-imino) -3-hexanonato-N, O, N ′) is larger than strontium and is therefore expected to be less volatile.

FIG. 2 is a schematic diagram showing the crystal structure of bis (2,2-dimethyl-5- (1-diethylamino-2-propylimino) -3-hexanonato-N, O, N ′) strontium. Bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium (solid line) vs. bis (2,2-dimethyl-5- ( Dimethylaminoethylimino) -3-hexanonato-N, O, N ') thermogravimetric analysis (TGA) diagram of strontium (dotted line), a new Sr complex with a chiral center (solid line) of two nitrogen atoms It is much more stable than one without a chiral center in between (dotted line), thus indicating little residue. FIG. 3 is a schematic diagram showing a crystal structure of bis (2,2-dimethyl-5- (1-dimethylamino-2′-propylimino) -3-hexanonato-N, O, N ′) nickel. Bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N ') nickel (solid line) vs. bis (2,2-dimethyl-5- ( (Dimethylaminoethylimino) -3-hexanonato-N, O, N ') Nickel (dotted line) thermogravimetric analysis (TGA) diagram showing the new Ni complex with a chiral center (solid line) of two nitrogen atoms The stability is much greater than that without a chiral center in between (dotted line), thus indicating that the residue remaining is less than 3%. FIG. 4 is a schematic diagram showing a crystal structure of bis (4- (1-dimethylamino-2-propylimino) -2-pentanonato) nickel. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) diagrams of bis (4-1-dimethylamino-2-propylimino) -2-pentanonato) nickel, a new Ni complex with a chiral center is volatile It shows that the residue is small and the melting point is low (˜100 ° C.). FIG. 2 is a schematic diagram showing the crystal structure of bis (2,2-dimethyl-5- (1-diethylamino-2-propylimino) -3-hexanonato-N, O, N ′) strontium. FIG. 2 is a schematic diagram showing the crystal structure of bis (2,2-dimethyl-5- (1-methylethylamino-2-propylimino) -3-hexanonato) strontium. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) of bis (2,2-dimethyl-5- (1-methylethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium The new Sr complex with a chiral center and an asymmetric substituent on the amino function shows that the residue is less than 5% and the melting point is low (˜133 ° C.) Yes. Bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium (solid line) and bis (2,2-dimethyl-5- (dimethyl) Aminoethylimino) -3-hexanonato-N, O, N ') is a graph comparing the vapor pressures of strontium (dotted line), where a new Sr complex with a chiral center (solid line) is chiral between two nitrogen atoms More volatile than those without center (dotted line) (however, the molecular weight of bis (2,2-dimethyl-5- (dimethylaminoethylimino) -3-hexanonato-N, O, N ') strontium Is smaller than bis (2,2-dimethyl-5- (1-dimethylamino) -2-propylimino) -3-hexanonato-N, O, N ′) strontium).

Claims (24)

A metal-containing complex represented by a structural formula selected from the group consisting of the following structural formulas (A) and (B):

Wherein M is a divalent to pentavalent metal group and R ¹ is selected from the group consisting of alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl containing ¹ to 10 carbon atoms. R ² is selected from the group consisting of hydrogen, alkyl, alkoxy, alicyclic group, and aryl; R ³ is selected from the group consisting of alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl; R ⁴ is a C _3-10 branched alkylene bridge having at least one chiral carbon atom, and R ⁵ and R ⁶ are each independently an alkyl, fluoroalkyl, alicyclic group, aryl, and any oxygen or nitrogen atom And n is an integer equal to the valence of the metal M); and

Wherein M is a metal ion selected from Group 4 and Group 5 metals, R ¹ is an alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group containing ¹ to 10 carbon atoms, and R ² is selected from the group consisting of aryl, R ² is selected from the group consisting of hydrogen, alkyl, alkoxy, alicyclic group, and aryl, and R ³ is selected from alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl. R ⁴ is a C _3-10 branched alkylene bridge having at least one chiral carbon atom, and R ⁵ and R ⁶ are independently alkyl, fluoroalkyl, alicyclic group, aryl, or is selected from the group consisting of heterocyclic group containing an oxygen or nitrogen atom, R ⁷ is selected from alkyl, fluoroalkyl, cycloaliphatic, and from the group consisting of aryl, m and n is at least , And the sum of m + n is equal to the valence of the metal M).   M is a group consisting of calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, vanadium, tungsten, manganese, cobalt, iron, nickel, ruthenium, zinc, copper, palladium, platinum, iridium, rhenium, and osmium. The metal-containing complex according to claim 1, which is represented by a structural formula (A) selected from: R ¹ is selected from t-butyl and t-pentyl, R ² is selected from the group consisting of hydrogen, methyl and ethyl, R ³ is selected from the group consisting of methyl and ethyl, and R ⁴ is C having a chiral center. _3. A metal-containing complex according to claim 2, wherein the metal-containing complex is a ₃ alkylene bridge, wherein R ⁵ and R ⁶ are independently selected from the group consisting of methyl and ethyl. M is strontium, R ¹ is t-butyl, R ² is hydrogen, R ³ is methyl, R ⁴ is methyl ethylene , and R ⁵ and R ⁶ are ethyl The metal-containing complex according to claim 3. M is strontium, R ¹ is t-butyl, R ² is hydrogen, R ³ is methyl, R ⁴ is methyl ethylene , R ⁵ is methyl, and R ⁶ is ethyl The metal-containing complex according to claim 3. M is cobalt, R ¹ is t-butyl, R ² is hydrogen, R ³ is methyl, R ⁴ is methyl ethylene , and R ⁵ and R ⁶ are methyl. The metal-containing complex according to claim 1. M is nickel, R ¹ is t-butyl, R ² is hydrogen, R ³ is methyl, R ⁴ is methyl ethylene , and R ⁵ and R ⁶ are methyl. The metal-containing complex according to claim 1.   The metal-containing complex according to claim 1, wherein M is represented by a structural formula (B) selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, and tantalum. R ¹ is selected from the group consisting of C _1-5 alkyl, R ² is selected from the group consisting of hydrogen, methyl, and ethyl, R ³ is selected from the group consisting of methyl and ethyl, and R ⁴ is at least one A C _3-4 alkylene bridge having a chiral center, wherein R ⁵ and R ⁶ are independently selected from the group consisting of methyl and ethyl, and R ⁷ is methyl, ethyl, propyl, isopropyl, n-butyl, sec- 9. The metal-containing complex according to claim 8, which is selected from the group consisting of butyl, isobutyl, and tert-butyl. M is Ti, R ¹ is methyl, R ² is hydrogen, R ³ is methyl, R ⁴ is a C ₃ alkylene bridge with one chiral center, and R ⁵ and R ⁶ are methyl The metal-containing complex according to claim 8, wherein M is Hf, R ¹ is methyl, R ² is hydrogen, R ³ is methyl, R ⁴ is a C ₃ alkylene bridge with one chiral center, and R ⁵ and R ⁶ are methyl The metal-containing complex according to claim 8, wherein M is Zr, R ¹ is methyl, R ² is hydrogen, R ³ is methyl, R ⁴ is a C ₃ alkylene bridge with one chiral center, R ⁵ and R ⁶ are methyl The metal-containing complex according to claim 8, wherein M is Ti, R ¹ is t-butyl, R ² is hydrogen, R ³ is methyl, R ⁴ is a C ₃ alkylene bridge, and R ⁵ and R ⁶ are methyl. The metal-containing complex according to claim 8, characterized in that: M is Hf, R ¹ is t-butyl, R ² is hydrogen, R ³ is methyl, R ⁴ is a C ₃ alkylene bridge with one chiral center, R ⁵ and R ⁶ 9. The metal-containing complex according to claim 8, wherein is a methyl. M is Zr, R ¹ is t-butyl, R ² is hydrogen, R ³ is methyl, R ⁴ is a C ₃ alkylene bridge with one chiral center, R ⁵ and R ⁶ 9. The metal-containing complex according to claim 8, wherein is a methyl. The metal-containing complex according to claim 1, glyme solvents, C ₂ -C ₁₂ alkanols, dialkyl ethers comprising C ₁ -C ₆ alkyl moiety, C ₄ -C ₈ cyclic ethers, C ₁₂ -C ₆₀ Crown O ₄ —O ₂₀ ethers (where the prefix C _i range is the number i of carbon atoms in the ether compound, and the post O _i range is the number of oxygen atoms in the ether compound) i) organic ethers selected from the group consisting of C ₆ -C ₁₂ aliphatic hydrocarbons, C ₆ -C ₁₈ aromatic hydrocarbons, organic esters, organic amines, polyamines and organic amides those dissolved in solvent selected from the group consisting of a solution of metals-containing complex. The solvent is selected from the group consisting of N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, N, N-diethylacetamide, and N, N-diethylformamide. The metal-containing complex solution according to claim 16, which is an organic amide. In a deposition process of introducing a precursor source and an oxygen-containing agent into a deposition chamber to deposit a metal oxide film on a substrate, forming a shape-matched metal oxide thin film on the substrate,
Vapor deposition process, wherein the precursor source is a metal-containing complex represented by a structural formula selected from the group consisting of the following structural formulas (A) and (B):

Wherein M is a divalent to pentavalent metal group and R ¹ is selected from the group consisting of alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl containing ¹ to 10 carbon atoms. R ² is selected from the group consisting of hydrogen, alkyl, alkoxy, alicyclic group, and aryl; R ³ is selected from the group consisting of alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl; R ⁴ is a C _3-10 branched alkylene bridge having at least one chiral carbon atom, and R ⁵ and R ⁶ are each independently an alkyl, fluoroalkyl, alicyclic group, aryl, and any oxygen or nitrogen atom And n is an integer equal to the valence of the metal M); and

Wherein M is a metal ion selected from Group 4 and Group 5 metals, R ¹ is an alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group containing ¹ to 10 carbon atoms, and R ² is selected from the group consisting of aryl, R ² is selected from the group consisting of hydrogen, alkyl, alkoxy, alicyclic group, and aryl, and R ³ is selected from alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl. R ⁴ is a C _3-10 branched alkylene bridge having at least one chiral carbon atom, and R ⁵ and R ⁶ are independently alkyl, fluoroalkyl, alicyclic group, aryl, or Selected from the group consisting of heterocyclic groups containing oxygen or nitrogen atoms, R ⁷ is selected from the group consisting of alkyl, fluoroalkyl, alicyclic groups, and aryl, and m and n are at least 1 and the sum of m + n is equal to the valence of metal M).   19. The vapor deposition process of claim 18, wherein the vapor deposition process is selected from the group consisting of chemical vapor deposition, plasma enhanced chemical vapor deposition, atomic layer deposition, and plasma enhanced atomic layer deposition. . Oxygen-containing agent, water, vapor deposition according to O _2, H ₂ O _2, ozone, O ₂ plasma, H ₂ O plasma, and claim 18, characterized in that it is selected from the group consisting of mixtures thereof process. In a deposition process of introducing a precursor source and a reducing agent into a deposition chamber to deposit a metal film on a substrate, forming a shape-matched metal thin film on the substrate,
Vapor deposition process, wherein the precursor source is a metal-containing complex represented by a structural formula selected from the group consisting of the following structural formulas (A) and (B):

Wherein M is a divalent to pentavalent metal group and R ¹ is selected from the group consisting of alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl containing ¹ to 10 carbon atoms. R ² is selected from the group consisting of hydrogen, alkyl, alkoxy, alicyclic group, and aryl; R ³ is selected from the group consisting of alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl; R ⁴ is a C _3-10 branched alkylene bridge having at least one chiral carbon atom, and R ⁵ and R ⁶ are each independently an alkyl, fluoroalkyl, alicyclic group, aryl, and any oxygen or nitrogen atom And n is an integer equal to the valence of the metal M); and

Wherein M is a metal ion selected from Group 4 and Group 5 metals and R ¹ is an alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group containing ¹ to 10 carbon atoms, and R ² is selected from the group consisting of aryl, R ² is selected from the group consisting of hydrogen, alkyl, alkoxy, alicyclic group, and aryl, and R ³ is selected from alkyl, alkoxyalkyl, fluoroalkyl, alicyclic group, and aryl. R ⁴ is a C _3-10 branched alkylene bridge having at least one chiral carbon atom, and R ⁵ and R ⁶ are independently alkyl, fluoroalkyl, alicyclic group, aryl, or R ⁷ is selected from the group consisting of heterocyclic groups containing oxygen or nitrogen atoms, R ⁷ is selected from the group consisting of alkyl, fluoroalkyl, alicyclic groups, and aryl, and m and n are at least 1 And the sum of m + n is equal to the valence of metal M).   The vapor deposition process of claim 21, wherein the reducing agent is selected from the group consisting of hydrogen, hydrazine, monoalkyl hydrazine, dialkyl hydrazine, ammonia, and mixtures thereof. In a deposition process of forming a metal oxide thin film on a substrate by introducing a precursor source solution and an oxygen-containing agent into a deposition chamber to deposit a metal oxide film on the substrate,
The deposition process includes glyme solvent, C ₂ -C ₁₂ alkanols, dialkyl ethers containing C ₁ -C ₆ alkyl moieties, C ₄ -C ₈ cyclic ethers, C ₁₂ -C ₆₀ crown O ₄ -O ₂₀ Ethers, where the prefix C _i range is the number of carbon atoms i in the ether compound and the postfix O _i range is the number of oxygen atoms i in the ether compound Organic ethers selected from the group, selected from the group consisting of C ₆ -C ₁₂ aliphatic hydrocarbons, C ₆ -C ₁₈ aromatic hydrocarbons, organic esters, organic amines, polyamines and organic amides A vapor deposition process using a solution containing the metal-containing complex according to claim 18 dissolved in a solvent. In a deposition process of introducing a precursor source solution and a reducing agent into a deposition chamber to deposit a metal film on the substrate, forming a shape-matched metal thin film on the substrate,
The deposition process includes glyme solvent, C ₂ -C ₁₂ alkanols, dialkyl ethers containing C ₁ -C ₆ alkyl moieties, C ₄ -C ₈ cyclic ethers, C ₁₂ -C ₆₀ crown O ₄ -O ₂₀ Ethers, where the prefix C _i range is the number of carbon atoms i in the ether compound and the postfix O _i range is the number of oxygen atoms i in the ether compound Organic ethers selected from the group, selected from the group consisting of C ₆ -C ₁₂ aliphatic hydrocarbons, C ₆ -C ₁₈ aromatic hydrocarbons, organic esters, organic amines, polyamines and organic amides The vapor deposition process characterized by using the solution containing the metal containing complex of Claim 21 melt | dissolved in the solvent.

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